Method for the removal of metal contaminants from petroleum residual stocks



Walter F. Lorene, Harvey, I1l., Carl D. Keith, Munster,

Ind., and William P. Hettinger, Jr., Dalton, lli., assignors to Sinclair Refining Company, New York, N.Y., a corporation of Maine No Drawing. Filed Sept. 6, 1957, Ser. No. 682,267

2 Claims. (Cl. 208-453) Our invention relates to a method for the removal of metal contaminants from petroleum residual stocks.

Petroleum residual stocks, such as topped crude, reduced crude, vacuum reduced crude, bottoms from the propane deasphalting of reduced crude and the like, almost invariably contain compounds of metals such as nickel and vanadium. The presence of such compounds in the residual oils render them much less desirable for use as such as fuels and also as feed stocks for further refinery processing wherein solid catalysts are utilized, inasmuch as they tend to contaminate the catalyst.

In accordance with our present invention we have discovered that hematite ores having a surface area of at least about 20 square meters per gram, and preferably at least about 30 square meters per gram, are very effective agents for use in the removal of metal compounds from petroleum residual stocks and we have devised a method whereby the metallic contaminants can be removed from such stocks with the aid of these hematite ores. The surface area of the ore can be as high as desired and a number of ores have areas falling in the range of about 20 to 100 square meters per gram. We accomplish the removal of the metal compounds by passing the petroleum residual stocks into contact with the hematite ore at a temperature within the range from 750 F. to 950 F. and at a pressure of from atmospheric to 3000 p.s.i.g. The residual stock is contacted with the hematite ore at a weight hourly space velocity (weight units of residual stock per weight unit of hematite ore per hour) of from 0.3 to 7.5 and the stock is contacted with the ore while the stock is in admixture with hydrogen in the amount of from 200 to 7000 standard cubic feet of hydrogen per barrel of residual stock. Preferably, the reaction temperature is within the range from 775 F. to 875 F., the reaction pressure is within the range from 500 p.s.i.g. to 1500 p.s.i.g., the weight hourly space velocity is within the range from 0.5 to 2 and the hydrogen rate is from 2000 to 4000 standard cubic feet of hydrogen per barrel of residual stock. In contacting the residual stock with the hematite, a fixed bed, a moving bed, a fluidized bed or a slurry system of hematite particles can be utilized, and in fixed bed and moving bed operation the mixture of hydrogen and feed stock can be passed downwardly or upwardly through the bed.

Not only is our process advantageous in that it eiiects removal of metal compounds from the oil, but it is also advantageous in that the liquid product recovery is high and, in comparison with the feed, is of increased API gravity and hydrogen content and of decreased sulfur and carbon value. Moreover, the practice of our process results in a relatively low production of coke. The hematite ore catalyst which we employ, although highly eflfective, is inexpensive, so that when it has become deactivated it can be discarded and replaced by a fresh quantity of ore. On the other hand, the catalytic material which we use, upon deactiavtion, can conveniently be regenerated to restore its activity by removal of col-re through burning.

2,951,035 Patented Aug. 30, 1960 The oil which has been treated with hydrogen in ac cordance with our invention in the presence of the hema- 'tite ore catalyst can be utilized as such as fuel or, on

the other hand, it can be employed as a feed stock for further refinery processing, such as hydrocracking in the presence of a catalyst composed of a mixture of cobalt oxide and molybdenum oxide supported on alumina to produce gasoline and other valuable products. For such an operation to be carried out, the eflluent from the reaction system in which our process is carried out can be simply introduced into a hydrocracking system, further amounts of hydrogen gas also being introduced into the hydrocracking system, if desired.

The following examples illustrate various embodiments which fall within the scope of our invention and further illustrate the practice there-of.

EXAMPLES 1 T0 IV The petroleum residual stock employed as the feed in the examples was a deasphalted oil produced from asphalt which was produced in the vacuum distillation of crude. To provide the deasphalted oil, the asphalt was extracted with a butane-pentane blend containing 42 volume percent of pentane to obtain 82 weight percent of the deasphalted oil, based upon the weight of the asphalt. The deasphalted oil contained 1.04 weight percent pentane insoiubles and had the characteristics set forth in Table I below. Table I also includes the characteristics of the asphalt which was extracted with the butane-pentane-blend in order to provide the deasphalted oil.

Kin. Vis. at 210 F. SUS- Viscosity, FV/210 F Viscosity, FV/275 F Insolubles in Benzena Insolubles in CO1; Insolubles in OSz. Insolubles in 110.; Molecular Weigh Percent Chloride... Emission Spec, ppm. Ni Emission Spec, p.p.m. V" Penetration, 77 F Ring and Ball, FTIIIIII:

In carrying out the various examples, the catalyst was charged to a heated one-inch diameter reactor. The void space above and below the catalyst bed was packed with solid glass beads, and glass wool plugs were employed to retain the catalyst particles in place. The reactor was sealed in place in a bronze block furnace, a hydrogen rate of approximately 5 standard cubic feet per hour at atmospheric pressure was established through the reactor and the heat to the furnace was turned on. The temperature was brought up to reaction temperature and held there for several hours, after which the system was pressured up with hydrogen to the desired pressure and hydrogen flow established.

The feed stock was then introduced at a predetermined rate, both the hydrogen and feed stock passing downwardly through the catalyst bed. A processing run of approximately 30-40 minutes was made in order to line out temperatures and rates and to establish steady state conditions. An attempt was made to split each experiment into four separate sections (A, B, C and 1)), each of approximately 20-30 minutes duration in order to folpheric pressure and before pressuring with hydrogen, was presulfided by passing hydrogen sulfide gas into contact with the ore at atmospheric pressure.

1 WEISV means weight hourly space velocity.

Table 11 Example I II III IV Fraction- A B A B O D Y A B C D A B 3 Cat lyst Description Iron Ore Iron Ore Iron Ore Presulfided Iron Ore (Hematite- (Hematite-Feioa) (Hematite-FezOa) (Hematite-Fem FezOa), 8-14 Mesh 8-14 Mesh 8-14 Mesh s-14 Mesh Conditions:

emp., F 805 805 859 855 852 850 750 750 750 750 805 805 805 Pressure, p.s.i g 1, 000 1, 000 l, 000 1, 000 1, 000 1, 000 1, 000 1, 000 1, 000 1, 000 1, 000 1, 000 1,000 V 1 0.9 1.0 1.0 1. 1.0 1.0 1.0 1.0 1. 1.0 1. 1.0 1.0 Hz Rate, s.c.f. 3, 780 3, 780 3, 780 3, 780 3, 780 3, 780 3, 780 3, 780 3, 780 3, 780 3, 780 3, 780 3, 780 Catalyst Charge, g 42 423 423 423 423 423 42 423 42 423 42 423 Direction of flow Downflow Downflow Downflow Downflow Recoveries, Wt. Percent-'Uncor- I rected:

0 95.3 92.6 97.4 05.7 Coke 2 2.5 3.2 1.2 1.9

Liquid Product-Analytical Results:

API Gravity .9 18.8 30. 7 24. 5 24. 3 22. 5 15. 7 15.0 14. 8 14. 7 18. 5 17.4 17. 4 Percent SulfuL 0.72 0.85 0.55 0. 50 0.61 0.72 1.19 1.26 1.40 1.44 0.98 V 1.16 1. 23 Percent Nitrogen 0.48 0. 57 0.38 0. 56 0. 51 0. 53 0v 43 0. 47 0. 46 0.42 0.45 0. 45 0.47 Ramsbottom Carbon 5. 82 2. 27 5. 14 5.12 6. 30 7. 40 8. 70 8. 51 9.10 7.27 7.82 7. 95 Emission Spec.

p.p.m. N 3. 7 5.1 2.1 2. 6 3.1 5.1 28 28 13 11 11 17.9111. V105 2. 9 5. 9 1. 3 1.4 1.3 2. 5 18 41 54 51 19 28 28 Percent C 86.07 85. 70 1 Percent H 11. 52 11.46 7

Virgin Cat-Area. mfl/g 69 69 69 69 69 H; Consumption, s.c.f./bbl 410 410 r 2 Coke may be high due to pump priming clijficulties; run terminated due to time limitations.

Run terminated due to a gauge failure.

4 Value of Ramsbottom carbon not obtained because of water interference.

low any change in demetalization activity of .the catalyst, as well as any change of other product properties. Some difiiculties were encountered, so that it was not possible in all cases to split the overall run into four sep- The data of Table III were gathered in additional runs conducted to demetalize the feed of Table 11 according to the procedure used in the other examples. Example V establishes that low surface area, e.g., 4 square meters, hematite ores are not eifective demetalizatio'n catalysts. In Examples VI and VII the demetalization was more eifective due to the use of ores of intermediate surface area, but still these ores are not as cfiective as those whose surface area exceeds about square meters per gram. Example VIII illustrates that iron ores which are substantially magnetic are materially less effective than the hematite ores.

Table 111 Example. V VI Fraction A B C D A B O D Catalyst Description Hematite-Fem; Hematite-Fem;

8-14 mesh 8'14 mesh, slightly magnetic Surface area, sq. mJgm 4 35 Conditions:

Temp, 805 805 805 805 805 805 805 Pressure, p 1,000 1,000 1,000 1, 000 1,000 1,000 1, 000 HSV... 1. 1.0 1.0 1. 0 1.0 1. 1. H2 rate, 5. 3, 780 3, 780 3, 780 3, 780 3, 780 3, 780 3, 780 Catalyst charge, g 423 423 423 423 423 423 Direction of flow. Dowuflow Downflow Liquid ProductAnal tical Results:

AP Gravity. 16.1 15.6 15. 2 18.2 17. 5 17.1 16. 9 Percent Sulfur 1. 63 1. 70 1. 71 1. 76 1. 07 1. 11 1. 24 1. 17 Percent Nitroge 0.60 0.09 0.60 0. 58 0. 56 0.64 0.58 0.56 Ramsbottom carbon 8.73 8. 70 9. 11 9. 44 7.09 7. 73 7. 8. 0? Emission spec.

p. p. m. NiO 44 42 44 47 20 22 24 25 p.p.m. V 0 100 100 64 66 92 86 Percent Carbon on catalyst 2. 74 1. 82 4. 64 3. 71

Table III-Contmued Example VII VIII Fraction A B O D A B O D Catalyst Description Hematite-Fem; Vermlllion Iron Ore 8-14 mesh 50% magnetic, 8-14 mesh Surface area, sq. mJgm 66 Conditions:

Temp., F 805 805 805 805 805 805 805 805 Pressure, 1) S i g 1, 000 1,000 1,000 1, 000 1, 000 1,000 1, 000 1,000 V 1. 1.0 1.0 1. 1.0 1.0 1.0 1.0 H. rate s.c.f./bb1 3, 780 3,780 3, 780 s, 780 3, 780 3, 780 3, 780 3,780 Catalyst charge, g 423 423 423 428 423 423 423 423 Direction of flow Downflow Downfiow Liquid Product-Analytical Results:

API Gravlty 18. 6 17.3 17. 3 16. 8 14. 8 15.0 14. 9 14. Percent Sulfur. 0. 89 1.09 1.17 1.23 1.50 1.66 1. 73 1.70 Percent Nitrogen. 0.55 0.58 0.60 0. 58 0. 60 0.56 0.61 0. 60 Ramsbottom carbon 6. 71 8.18 8.05 8. 23 9. 93 9. 77 9. 97 9. 80 Emission spec.

p.p.m. N 16.2 19.7 21.8 26.4 55. 5 60 64 64 p.p.m. V90 25. 6 51. 4 72.0 81.0 163 145 140 140 Percent Carbon on catalyst 4. 56 2.74 1. 85 0.65

We claim:

1. A method for the removal of metallic contaminants from a petroleum residual stock containing the same which comprises passing the stock into contact with non-magnetic hematite ore having a surface area of at least about square meters per gram at a temperature of from 750 F. to 950 F., a pressure of from atmospheric to 3000 p.s.i.g. and at a weight hourly space velocity of from 0.3 to 7.5 While the stock is in admixture with hydrogen in the amount of from 200 to 7000-standard cubic feet per barrel.

2. A method for the removal of metallic contaminants from a petroleum residual stock containing the same which comprises passing the stock into contact with nonmagnetic hematite ore having a surface area of at least 5 to 2 while the stock is in admixture with hydrogen in the amount of from 2000 to 4000 standard cubic feet per barrel.

References Cited in the file of this patent UNITED STATES PATENTS 1,882,000 Cross Oct. 11, 1932 2,614,067 Reed et a1. Oct. 14, 1952 2,717,855 Nicholson Sept. 13, 1955 FOREIGN PATENTS 735,520 Great Britain Aug. 24, 1955 

1. A METHOD FOR THE REMOVAL OF METALLIC CONTAMINANTS FROM A PETROLEUM RESIDUAL STOCK CONTAINING THE SAME WHICH COMPRISES PASSING THE STOCK INTO CONTACT WITH NON-MAGNETIC HEMATITE ORE HAVING A SURFACE AREA OF AT LEAST ABOUT 20 SQUARE METERS PER GRAM AT A TEMPERATURE OF FROM 750*F. TO 950*F., A PRESSURE OF FROM ATMOSPHERIC TO 3000 P.S.I.G. AND AT A WEIGHT HOURLY SPACE VELOCITY OF FROM 0.3 TO 7.5 WHILE THE STOCK IS IN ADMIXTURE WITH HYDROGEN IN THE AMOUNT OF FROM 200 TO 7000 STANDARD CUBIC FEET PER BARREL. 